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Synthese Und Photochemie Von Iso(Thio)Cumarinen

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Synthese Und Photochemie Von Iso(Thio)Cumarinen Synthese und Photochemie von Iso(thio)cumarinen Dissertation zur Erlangung des Doktorgrades des Fachbereichs Chemie der Universität Hamburg vorgelegt von Michael Kinder aus Solingen Hamburg 2001 Synthese und Photochemie von Iso(thio)cumarinen Dissertation zur Erlangung des Doktorgrades des Fachbereichs Chemie der Universität Hamburg vorgelegt von Michael Kinder aus Solingen Hamburg 2001 Die vorliegende Arbeit wurde in der Zeit von Juli 1997 bis Dezember 2000 unter der Leitung von Herrn Prof. Dr. P. Margaretha im Institut für Organische Chemie der Universität Hamburg durchgeführt. Für die Überlassung der interessanten Aufgabenstellung dieser Dissertation sowie für die hilfreiche Unterstützung und die fortwährende Diskussionsbereitschaft möchte ich mich bei meinem Doktorvater, Herrn Prof. Dr. P. Margaretha, herzlichst bedanken. 1. Gutachter: Prof. Dr. P. Margaretha 2. Gutachter: Prof. Dr. W. A. König Tag der mündlichen Prüfung: 24. April 2001 Meinen Eltern gewidmet Inhaltsverzeichnis A Allgemeiner Teil.....................................................................................1 1. Einleitung...................................................................................................................1 2. Vorkommen, Aktivität und Anwendung von Isocumarinen und Isothiocumarinen ......................................................................................................3 3. Vergleich der Photochemie von Isocumarinen, Isothiocumarinen, Cumarinen und Thiocumarinen ..................................................................................................9 4. Aufgabenstellung ....................................................................................................15 B Hauptteil ...............................................................................................16 1. Darstellung der Photoedukte .................................................................................17 1.1 Allgemeine Konzepte und Synthesestrategien .....................................................17 1.2 Verwendeter Syntheseweg .....................................................................................18 1.2.1 Übersicht...................................................................................................................18 1.2.2 Darstellung der 2-Phenylethanole.............................................................................20 1.2.3 Darstellung der Methoxyethoxymethyl-ether...........................................................21 1.2.4 Darstellung der Isochromane ....................................................................................24 1.2.5 Darstellung der Isochroman-1-one ...........................................................................28 1.2.6 Darstellung der Isocumarine.....................................................................................30 1.2.7 Darstellung der 2-(2’-Benzylthioethyl)-benzoesäuren .............................................33 1.2.8 Darstellung der Isothiochroman-1-one .....................................................................36 1.2.9 Darstellung der Isothiocumarine...............................................................................38 1.3 Spektroskopische Eigenschaften der dargestellten Photoedukte .......................42 1.3.1 1H- und 13C-Kernresonanz-Spektroskopie................................................................42 1.3.2 Massenspektrometrie ................................................................................................44 1.3.3 UV-Vis- und Fluoreszenz-Spektroskopie.................................................................44 1.3.4 Polarographie und Cyclovoltammetrie .....................................................................49 2. Photochemische Untersuchungen..........................................................................52 2.1 Allgemeine Grundlagen der Photochemie............................................................52 2.2 Bestrahlungen der Isocumarine ............................................................................57 2.2.1 Bestrahlungen in Lösung ..........................................................................................57 2.2.2 Bestrahlungen in Festphase ......................................................................................64 2.2.3 Bestrahlungen in Lösung mit Alkenen .....................................................................66 2.3 Bestrahlungen der Isothiocumarine......................................................................76 I Inhaltsverzeichnis 2.3.1 Bestrahlungen in Lösung.......................................................................................... 76 2.3.2 Bestrahlungen in Festphase...................................................................................... 77 2.3.3 Bestrahlungen in Lösung mit Alkenen..................................................................... 83 3. Diskussion und Vergleich der Bestrahlungsergebnisse ...................................... 86 C Zusammenfassung................................................................................93 D Abstract.................................................................................................98 E Experimenteller Teil ..........................................................................100 1. Geräte und Methoden .......................................................................................... 101 2. Synthesen der Photoedukte ................................................................................. 103 2.1 Synthesen von 5-Methylisocumarin (1b) und 5-Methylisothiocumarin (2b).. 103 2.1.1 Synthese von 2-(2'-Methylphenyl)-ethanol............................................................ 103 2.1.2 Synthese von 9-(2'-Methylphenyl)-2,5,7-trioxanonan ........................................... 104 2.1.3 Synthese von 5- Methylisochroman....................................................................... 105 2.1.4 Synthese von 5-Methylisochroman-1-on ............................................................... 106 2.1.5 Synthese von 4-Brom-5-methylisochroman-1-on.................................................. 107 2.1.6 Synthese von 5-Methylisocumarin......................................................................... 107 2.1.7 Synthese von 2-(2'-Benzylthioethyl)-3-methyl-benzoesäure................................. 108 2.1.8 Synthese von 5-Methylisothiochroman-1-on ......................................................... 109 2.1.9 Synthese von 4-Brom-5-methylisothiochroman-1-on............................................ 111 2.1.10 Synthese von 5-Methylisothiocumarin................................................................... 111 2.2 Synthesen von 7-Methylisocumarin (1c) und 7-Methylisothiocumarin (2c)... 113 2.2.1 Synthese von 2-(4'-Methylphenyl)-ethanol............................................................ 113 2.2.2 Synthese von 9-(4'-Methylphenyl)-2,5,7-trioxanonan ........................................... 114 2.2.3 Synthese von 7-Methylisochroman........................................................................ 115 2.2.4 Synthese von 7-Methylisochroman-1-on ............................................................... 115 2.2.5 Synthese von 4-Brom-7-methylisochroman-1-on.................................................. 117 2.2.6 Synthese von 7-Methylisocumarin......................................................................... 118 2.2.7 Synthese von 2-(2'-Benzylthioethyl)-5-methyl-benzoesäure................................. 119 2.2.8 Synthese von 7-Methylisothiochroman-1-on ......................................................... 120 2.2.9 Synthese von 4-Brom-7-methylisothiochroman-1-on............................................ 121 2.2.10 Synthese von 7-Methylisothiocumarin................................................................... 122 II Inhaltsverzeichnis 2.3 Synthesen von 5-Trifluormethylisocumarin (1c) und 5-Trifluormethylisothiocumarin (2c) ..................................................................123 2.3.1 Synthese von 9-(2'-Trifluormethylphenyl)-2,5,7-trioxanonan................................123 2.3.2 Synthese von 5-Trifluormethylisochroman ............................................................124 2.3.3 Synthese von 5-Trifluormethylisochroman-1-on....................................................125 2.3.4 Synthese von 5-Trifluormethylisocumarin .............................................................126 2.3.5 Synthese von 2-(2'-Benzylthioethyl)-3-trifluormethyl-benzoesäure ......................128 2.3.6 Synthese von 5-Trifluormethylisothiochroman-1-on .............................................129 2.3.7 Synthese von 4-Brom-5-trifluormethylisothiochroman-1-on.................................130 2.3.8 Synthese von 5-Trifluormethylisothiocumarin.......................................................131 2.4 Synthesen von Benzo[f]isocumarin (1e) und Benzo[f]isothiocumarin (2e)......133 2.4.1 Synthese von 2-(1-Naphthyl)-ethanol.....................................................................133 2.4.2 Synthese von 9-(1'-Naphthyl)-2,5,7-trioxanonan ...................................................134 2.4.3 Synthese von 1,2-Dihydro-4H-naphtho[2,1-c]pyran ..............................................135 2.4.4 Synthese von 1,2-Dihydro-4H-naphtho[2,1-c]pyran-4-on .....................................136 2.4.5 Synthese von 4H-Naphtho[2,1-c]pyran-4-on .........................................................137 2.4.6 Synthese von 1-(2'-Benzylthioethyl)-naphthyl-2-carbonsäure
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